Monoazo dye



Patented May 17, 1949 UNITED STATES PATENT OFFICE MONOAZO DYE Joseph B. Dickey, Rochester, N. Y., and James. G.

McNally, Oak Ridge, Tenn, assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application February 23, 1945, Serial No. 579,494

1 Claim. 1

This invention relates to new azo compounds useful as colorants. The present application is a continuation-in-part of our prior application Serial No. 343,264, filed'Jnne 29, 194.0,now'Patent Number 2,373,700.

The azo compounds of our invention can be represented by the general formula:

CHCHgCOOCHr X form such as -alacquer form. Lacquersthat may be colored includafor example, those made. of or containing organic derivatives of cellulose as well as those made from vinyl resins such as vinyl acetate, vinyl chloride and methyl-methacrylate..

Coloration can be effected by dyeing; printing, stenciling or any other suitable methods The method of coloration-selected, as welrknown to those skilled in the art, will depend upon the form of the material to be colored and the efiect desired.

Dyeings of excellent fastness to light are obtained on organic derivatives of cellulose textile materials, particularly cellulose acetate textile materials. These dyeings are also characterized by good fastness to washing. Further the dye compounds of our invention dye cellulose. acetate and organic derivatives of cellulose in general rapidly, possess good tinctorial power therefor. and exhaust. well.

The colorations obtained with the dye compounds of our invention range from yellowishorange to reddish-orange. Yellowish-orange colors are obtained when the member X is halo..- genwhile reddish-orange colors are. obtained when X is methyl or. ethyl. "When X is hydrogen an orange color intermediate of yellowish-orange and reddish-orange is obtained.

The azo compounds of our invention likewise yield. dyeings on, cellulose:acetate textile materials. andorganic. derivatives of cellulose textile materials. generally which are definitely superior with respect to light fastness to dyeings obtained with dyes. having. an exactly similar structure ex ether and vinyl resin lacquers.

cent that the ester group attached to the amino group of the coupling component is -CH2COOCH3 rather than --CHzCHzCOOCI-Ia or -oHoHzooooH,

as in the present instance. This surprising and important difference could not have been pre dicted.

It is an object of our invention to provide a new class of azo compounds suitable for the coloration of organic derivatives of cellulose, nylon, vinyl acetate-vinyl chloride co-polymers and lacquers such as cellulose ester, cellulose Another object of our invention is to provide colored textile materials which are of excellent fastness to light and of good ,fastpess to washing. A particular object of our invention is to provide a new class of azo dyes suitable .for the coloration of cellulose acetate textile materials.

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose vpropionate or cellulose butyrate and the hydrolyzed as well as the, unhydrolyzed mixed organic acid esters of cellulose such as cellulose acetate-propionate, cellulose acetate-bu-tyrate and the cellulose ethers such as methyl cellulose, ethyl cellulose or benzyl cellulose. While our invention will be illustrated more particularly in connection with the coloration of cellulose acetataa material to which the invention is especially adapted, it will be understoodthat t applies to the coloration. of other organic derivatives of cellulose such as those just named as well as to the coloration of the other materials, mentioned herein.

The azodye compounds of our invention can. b prepared by .diazotizing, p-nitroaniline and ouplin the diazonium compound obtained withthe coupling compounds having the general formula:

lOQHCHzC OOCH;

Example 1 138: grams (1 gram mole) of p-nitroaniline-are heated at 60 C. in a mixture of 163 grams ofsul furic acid (95%) and 200 cc. of water until the amine has dissolved following which the reaction mixture resulting is poured onto 300 grams of ice with vigorous stirring. The p-nitroaniline is then diazotized by adding all at once a solution of 80 grams of sodium nitrite in 250 cc. of water. Upon completion of the diazotization reaction the excess nitrous acid present is destroyed by adding grams of urea.

Concurrently with the preparation of the diazo solution 265 grams (one gram mole) of the dimethyl ester of N-bis (p-carboxyethyl) aminobenzene are dissolved in a mixture consisting of 300 cc. of water, 56 grams of 95% sulfuric acid and 300 grams of ice. The diazo solution prepared above is then added with stirring and after a short time sodium carbonate is slowly added until the reaction mixture is just acid to litmus. The reaction mixture is tested for the presence of the diazo compound, with ,B-naphthol paper for example, and if no diazo compound is present, enough is added to just utilize any unreacted coupling component. The proper amount to be added can be determined by the p-naphthol test just mentioned as the presence of any free diazo compound can be readily detected by this test. Upon completion of the coupling reaction which takes place, the dye compound formed is recovered by filtration, washed with water and dried. The yield of dye exceeds 99%. The dye compound obtained has the formula:

CHnCHzC O OCH;

CHzCHzC O O OH- Ewample 2 138 grams (1 gram mole) of p-nitroaniline are diazotized and the diazonium compound obtained is coupled with 237 grams (1 gram mole) of the methyl ester of N-p-carboxy-a-methyl-ethyl-N- p-hydroxyethyl aminobenzene. The diazotization, coupling and dye recovery operations are carried out in accordance with the procedure described in Example 1. The dye compound obtained has the formula:

CHzCHzOH CHCHzC O OCH:

Example 3 OHQCHzOH l CHzCHzCOOCH;

The following tabulation further illustrates the azo compounds included within the scope of our invention. Th diazotization, coupling and recovery operations involved in the preparation of these dye compounds can be carried out in accordance with the procedure described hereinbefore.

Examples I C H: C Hi 0 H ongonzoooom I CHzCHzOH CHQCHOHOHZOH CHzCHzC O O CH;

chemo o OCH; $5. 14.

NOON-:IQ NwHomo 0 00m CHgCHOHCH;

( CHzCHzCOOCH! CHaCHzC O OCH| CHCHQCOOCHI CHaCHzC 0 OCH;

CHiCHgC O OCH;

omomomon 0110310 oocrn ta.

CH2CH2C O OCH:

GHaCHOHCH;

CH2CH2C O O OH| /CH2CH2OH (l: CHCHzCOOCHl OHzCHzOH CHaCHOHCHnOH CHzOHzCOOCH;

(1311 C HgC O O C H;

The compounds specifically disclosed herein are intended to be illustrative and not limitative of 0. v nt n as othe omo nds W th n e scope. of the invention can be prepared.

n r e ha e er peraiioe of the etc 9 1 e nqs. 9f nvention m be. Gnu-R clear 1 P p r on 0? 1 9 0 91 1 8. co p ime t us in their manufacture. is given hereinafter.

A. Preparation ofdimethyl ester of N-ln's (fi-carboxyethyl qminobenzene 93v grams (1 gram mole) ofaniline, 125 grams (1 .25. gram mole) of methyl crotonate cn crn=cncoocno and 11) cc. of glacial acetic acid wereheated together in a suitable. reaction vessel on a steam bath for 77 hours. On fractionation of the reaction mixture under reduced pressure (e. g. 9 mm.) the methyl ester of N-fi-carboxy-a-methyh ethyl aminobenzene boiling at 144-146 C./9 mm. is, obtained. The yield was- 58 grams or 30% of theory.

193 grams (1 grammole) of the methyl ester of N-p-carboxyl-a-methyl-ethyl aminobenzene are heated with 48.4 grams (1.1 gram mole) of ethylene oxide at 180 C. in a shaking autoclave for 6 hours. When cool the; reaction mixture is removed from the autoclave and distilled under reduced pressure (e. g. 9 mm.) to give a good yield of the methyl ester of N-fi-carboxy-amethyl-ethyl-N 3 hydroxyethylaminobenz ene having the formula: CH2CH2OH N onomcooom and boiling at 195202 C./9 mm.

C. Preparation of methyl ester of N-p-carbomyethyZ-N-p-hydromyethyl-3-chloro-aminobenzene 127.5 grams (1 gram mole) of m-choroaniline, 129 grams (1.5 gram mole) of methylacrylate and 10 cc. of glacial acetic acid are heated together in a, suitable reaction vessel on a steam bath for 72 hours. On fractionation of the reaction mixture at reduced pressure (e. g. 3 mm.) the methyl ester of N- 3-carboxyethyl-3-chloro-aminobenzene. boiling at 135-137" C./3 mm. is obtained.

-257.5 grams (1 gram moleoi the methyl ester of N-p-carboxyethyl-3-chloro-aminobenzene are heated with 48.4 grams (1.1 gram mole) of ethylene oxide at 180 C. in ashaking autoclave for 6 hours. When cool the reaction mixture is re.- moved from the autoclave and distilled under re,- duced pressure (e. g- 3 mm.) to give a good yield of the methyl ester of N-fi-carboxyethyl-N-p-hydsqxr t y hl rmamino nzene having he formula can: t H

and'boilingat 190-493 C./3 mm.

D. Preparation of the methyl ester of N-e-carbow ethyl-N-fi 'Y-dihydroxypropyl- 3 bromoaminobenzene 172 grams (1 gram mole) of m-bromoaniline, 86 grams (1 gram mole) of methyl acrylate and 8 cc. of glacial aceticacid are. heated together at 9-6-98" C- n the m. th for 6. ho r he acetic acid was then neutralized, with NaHClOs and the reaction mixture extracted with ether. The ether-layer was washedwith water, the ether removed by distillation under reduced pressure on a Water at a he. emainin o l iq d. d il und a pr ssure i 3 mm- A. y e d of he meth l ste -fi-car oxre hy -fitremor emieoben en bo lin at 1 .7- .0 0J3 mm, s ob a ned.

z rem 52 strain mo e) i th m t este of Nrlil x fi hylriiebromqe minebena ne. 66 grams (.6 gram mole), oiglycerol monochlorohy, dr n 1CH2C -IOI'ICH2QH1 and;51-.6. grams (figram mole of NaI-IC'Oa are. heated at 145 C. with stirring for 5 hours in anoil bath. The reaction mixture is cooled to C'. and 100 ,cc. of Water and 100 cc. of benzene are added. The oil layer s ashed t waten a d e eir-Zanev remov d by distillation under reduced pressure on a water bath. The viscous liquid remaining, consisting essentially of the methyl ester of N-fl-carboxyethyl-N-e'y-dihydroxypropyl 3 bromo aminobenzene having. the formula CHQCHOHOHROH CHzC H20 0 0 CH was. stt d r se wi hvu cfurthe stillation. E. Preparation of the dimethyl ester of-N'.8-c arboxyethyl-N-fi-carboxy-a-methyl ethyl aminobenzene CHzCHzCO 0 CH5.

F. Preparation of the methyl ester of N-e-carboxy.-ae th lth l -ryd rzipr ry mi-v nobeneene.

19.3 grams (.1 gram mole) of the methyl ester f N-flar xy -m thy r t yl m no enze e. 11.2.grams (.12 gram mole) ottrimethylenechlorohydrin, lpgrams (.12grarnmole) oi Nal-ICO;

and; 25 cc. oi to1uene- .were refluxed together for 8 he sw thstirr s, tter eel etto. 1.00 G- .25

heated to 140 C.

hydrin are then added dropwise with stirring over "cc. of water were added to the reaction mixture.

The water layer was drained off, the toluene fraction washed with water, and the water layer formed removed by draining. The toluene fraction was then distilled under a reduced pressure of mm. to recover the methyl ester of N-p-carboxy-a-methyl-ethyl-N- -hydroxypropyl aminobenzene having the formula:

CHCHZCOOCHB and boiling at I'M-178 C./5 mm. It will be understood, of course, that the toluene is recovered in the earlier stages of the distillation.

G. Preparation of the methyl ester of N-p-carboxyethyl-N-p-hydroxyethyl aminobenzene CHzCHzOH CHzCHzC OOCH;

and boiling at PIG-175 C./2 mm. is obtained.

H. Preparation of the methyl ester of N-p-carbowyethyl-N-c-hydroryethyl-B-methyl aminobenzene By the substitution of an equivalent molecular weight of meta toluidine for aniline in reaction A the methyl ester of N-fi-carboxyethyl-B-methyl aminobenzene can be obtained. When this compound is reacted with ethylene oxide in accordance with the procedure described, for example, in reaction G the methyl ester of N-fi-carboxyethyl-N-fi-hydroxyethyl-3-methyl aminobenzene boiling at 168-170 C./3 mm. is obtained.

I. Preparation of the methyl ester of N-B-carbomyethyl-N-B-hydroaryethyl 3 ethyl aminobenzene This compound can be prepared by substituting an equivalent molecular weight of meta ethylaniline for meta toluidine in the preceding reaction.

J. Preparation of the methyl ester of N-p-carboayethyZ-N-p-hydroxypropyl-3-ethyl aminobenzene This compound can be prepared by reacting meta-ethylaniline with methyl acrylate, recovering the methyl ester of N-fi-carboxyethyl-3-ethyl aminobenzene thus formed and reacting it with propylene oxide. The reactions above indicated as well as the recovery operations involved can be carried out in accordance with the procedure indicated in Examples A to I inclusive.

K. Preparation of the methyl ester of N-B-carboxy-a-methyl ethyl- N -,8,'ydihydroxyprom/l aminobenzene 21 grams of the methyl ester of N-fl-carboxya-methyl-ethyl aminobenzene and grams of sodium bicarbonate are mixed together and 13 grams of glycerol chloroa period of 30 minutes while maintaining a temperature of about C. Heating is continued until no more carbon dioxide is evolved. Upon cooling water is added to dissolve out water-soluble salts in the reaction mixture and after settling the water layer is drawn ofi. The reaction mixture remaining is then treated with benzene following which it is subjected to distillation to remove the Water and benzene present. On evaporation to relative dryness the desired product is obtained as a brown, heavy, viscous oil. This oil cannot be distilled without some decomposition but since it consists almost entirely of the desired product, purification is not essential. The compound obtained is soluble in most organic solvents as well as in dilute hydrochloric acid and dilute sulfuric acid. We would here note that the coupling compounds of our invention containing a pp -dihydroxylpropyl group are subject to decomposition when distilled and therefore one should not attempt to purify these compounds by distillation. Some pyrolysis of the fi,' -dihydroxypropyl group appears to take place on distillation.

By following the procedures set forth in Examples A to K, inclusive, the following coupling compounds, for example, can be prepared: The methyl ester of N-{i-carboxy-u-methyl-ethyl-N- p-hyd roxypropyl aminobenzene (B. P. 203-206 C./ 'l mm.); the dimethyl ester of N-bis-(e-carboxyethyl)-3-methyl aminobenzene (B. P. 169 C./3 mm.) the methyl ester of N-p-carboxyethyl-N-v-hydroxypropyl 3 bromo-aminobenzene; the methyl ester of N-B-carboxyethyl-N- B-hydroxypropyl aminobenzene (B. P. -185 C./1 mm); the dimethyl ester of N-bls S-carboxy-a-methyl-ethyl)-3-chloro aminobenzene; the methyl ester of N- S-carboxy-a-methyl-ethyl- N-5-hydroxyethyl-3-ethyl aminobenzene and the methyl ester oi N-[i-carboxyethyl-N-B-hydroxyethyl-3-fiuoro aminobenzene.

While the use of glacial acetic acid has been referred to in the reactions describing the preparation of the coupling compounds of our invention it is here noted that the use of glacial acetic acid is not essential as acetic acid of lesser strength can be used. However, the use of glacial acetic acid or highly concentrated aqueous acetic acid solutions appears desirable.

The azo compounds of our invention may beadvantageously directly applied to the textile material undergoing coloration in the form of an. aqueous suspension which can be prepared bygrinding the dye to a paste, in the presence of a.

sulfonated oil soap, or other suitable dispersing: agent and dispersin the resulting paste in water. Direct dyeing operations can, with advantage, be conducted at temperatures of about 70 C. to 85 C., but any suitable temperature may be used. Thus the textile material to be dyed or colored is ordinarily added to the dyebath at a temperature lower than that at which the main portion of the dyeing is to be effected, e. g. a temperature of from 45 to 55 C. Following this the temperature is raised to that selected for carrying out the operation. The temperature at which the process is carried out may vary somewhat, depending upon the particular material undergoing coloration. As understood by those skilled in the art, the intensity of dyeing can be varied by varying the proportion of dye to the material undergoing preparation. Generally speaking, 1 to 3 per cent by weight of the dye to material is employed, although any desired proportions can be used.

Suitable dispersing agents are disclosed in U. S. Patent 2,115,939, issuing April 26, 1938. The process dis-closed the aforesaid patent for the dyeing of cellulose acetate can be used in applying the dyes in the present invention to cellulose acetate. While satisfactory method for dyeing has been disclosed herein, it will be understood that any other suitable methods for dyeing the non-vegetable textile materials named herein can be employed. Lacquers may be colored. with the dye compounds of our invention by the methods customarily employed in the lacquer art.

The term nylon is intended to describe a linear polyamide resin such as forth in United States Patent 2,971,259, dated Februar- We would here note that the process described for the introduction of the Cl-lzCHsCOOCHs and the groups is not restricted to the coupling compounds disclosed herein but is generally applicable to aniline and its derivatives. To illustrate is applicable wherein the member X also represents an alkoxy group, an acylamino group or an alkyl group having more than one carbon atom. Similarly the member B may also represent delta hydroxybutyl, an alkoXyalkyl group or a hydroxyalkoxyalkyl group, such as ,B-hydroxy-pethoxyethyl, for example. The compounds just indicated can be used as coupling components in the preparation of azo dyes. They can, for ex- 10 ample, be coupled with diazotizeol p-nitroaniline to form azo compounds suitable for the coloration of cellulose carboxylic ester textile materials.

We claim: The azo compound having the formula:

/CH2CH2C O OCHa JOSEPH B. DICKEY. JAMES G. MCNALLY.

CHzCHgC OOCH;

REFERENCES CITED The following references are of record in the file oi this patent:

UNITED STATES PATENTS 

